Fast yellow sulfid dyestuffs.



UNITED STATES, PATENT OFFICE.

RICHARD HEBZ, OF FRANKFORT-ON-THE-MAIN, AND WILHELM FROHNEBERG, 0F

FECHENHEIM, GERMANY, ASSIGNOBS TO CASSELLA. COLOR COMPANY, A CORPORA- TION OF NEW YORK.

FAST YELLOW SULFID DYESTUFFS.

No Drawing.

To all whom it may concern Be it known that we, RICHARD Huuz,

Ph. 1)., a subject of the King of Prussia,

serviption.

e have found that if acetylated am no compounds of earbazole of the following general formula 1 i Y T T c G C O C U )0 C i Y Y where X means: hydrogen, or alkyl, or andkyl and Y means: hydrogen, or NllLCOCII or halogen, are heated with sulfur, preferably in presence of bcuzidin, tolidin or similarly acting substances at elevated temperatures, new sulfid colors result, which are distinguished by their fastues-s to chlorin. Especially valuable dyestuffs are Produced from the halogen derivatives of tie acetylalcd amino compounds.

The production of nitroand amino-compounds of carbazole has already been described in literature (villa Beilsteiu, 3rd edition, volume 4, pages 391, 901, 1172). The hitherto unknown nitroand amino-(N)-alkyland (N)-aralkylcarbazoles may be prepared in an analogous manner.

The halogen derivatives of the acetylated aminocarbumles and (N?-alkylcarbazoles may be made by either of t 10 two following general methods: Either the halogen may first be introduced into the nucleus of the carbazole, and the resulting halogen carbazoles then uitrated, reduced and acetylated, or the carbazole and its derivatives, substituted Specification of Letters Patent.

Application tiled February 21, 1918. Serial No. 749,847.

Patented J une 23, 1914.

in the NH group, are first nitrated, then chlorinated or brominated and the nitrohalogen compounds thus produced are then reduced and acetylated by the usual methods. Two series of isomeric halo en derivatives of amino, nitroaminoant diaminocarbazoles and (N)-alkylcarbazoles are obtained, which yield very valuable dyestuil's when heated with sulfur to high temperatures preferably in presence of beuzidin.

The process of manufacture is illustrated by the following examples:

Example I: 100 kilos diaeetyldiaminoearbazole (obtained by acctylating diami'noearbazole of the D. It. P. 46438), 200 kilos finely round sulfur, 100 kilos benzidin are heated in the stove for a prolonged period for instance 10 to 14 hours to 180250 C. The melt, when cold, is finely pondered and digested with a concentrated solution of sodium sulfid crystals at 90120 C. until a test proves to be easily soluble in a dilute hot sodium sulfid solution. This dyestuif possesses a great tiuctorial power, and dyes cotton ellow shades. Such dyeings are fast to was ling, light and chlorin.

If in the above example the diacetyldiaminm-arbazole is substituted by the same quantity of diac'etyldiamino-(N)-alkylearbazole (produced in an analogous manner from the (N)-alkylearbazole as described in the D. R. 1. 46438 from thecarbazolo) otherwise working" as above described, products are obtained of very similar properties, but of a somewhat more reddish shade.

Example II: kilos monoacetyhnonoamimmn'bazole (produced by acelylatin 2-3- amiumairbazole), :30 kilos benzidin, .200 lfllUS sulfur are melted, and healed as described in Example I. Thus a dyestuil is obtained dyeing cotton from a sodium sulfid bath or from a hydrosulfite vat greenish-yellow shades.

Example III: 50 kilos nitrmicetylaminocurbazole obtained by partly reducing dinitroearbazo e to nitroamiuocarbazole and acct ylating the latter), 30 kilos benzidin, 200 kilos sulfur are heated for 10 hours in the stove to 200-240 C. and then further treated as stated above. The resultin dyestufi dyes cotton greenish-yellow-olive s ades.

When substituting the nitroacetylaminoearbazole by the corresponding compound of the (N)-ethylcarbazole, very sinn or dyestuffs may be obtained.

10x: mple IV: 100 kilos of dichlordiacetyldiamiiw-carbazole Sproduced by nitrating, reducing and acety atiug the dichlorcarbazole, described by Mazzura and Lamberti in the 00.2. U/tint. Q6, 9., page 240), 100 kilos of benzidin, 250 kilos of sulfur, are treated as described in Exam lo I. The dyestuff 'irodueed dyes cotton c irectly greenish-yellow-olive shades, possessing excellent fastness to washing, light and bleaching, If in this example the dichlordiacetyl iaminocarbazole is replaced by the same amount of dichlordiacety diamlno (N) ethylcarbazole,

prepared 1n an analogous manner as above described, a similar coloring matter is obtained dyeing a somewhat more yellowish shade.

Example V: 00 kilos dichlordiacetyldiaminocarbazole (produced by acetylating the dichlordiaminocarbazole described by 1. Ziersch in the Reports of the German Chemicol Society, vol. 42, page 3799), 60 kilos benzidin, 200- kilos flowers of sulfur, are heated for a prolonged period, for instance 10 to 15 hours at 180-230 0.; the melt is then treated as above described. The d estulf produced dyes cotton in a sodium su id solution or in an alkaline hydrosulfite solution, yellow.

Exannle VI: 50 kilos of chloracetylamino-( )-alkylcarlm'/.ole (produced by first mononitrating (N)-alkylcarbazole in a glacial acetic acid solution, and then thorougly chlorinating the nitro body thus obtained, and finally reducing and acetylating it), 40 kilos benzidin, 180 kilos flowers of sulfur are heated and treated as described in the foregoing example. The dyestuff produced dyes cotton pure greenish-yellow shades of excellent fastness to washing and bleaching.

Having now particularly described and ascertained the nature of our said invention, and in what manner the same is to be performed, we. declare that what we claim is 1. The process for the manufacture of fast yellow sulfur dyestuffs, which consists in heating with sulfur at elevated tcm eratures in the presence of benzidin acety ated amino compounds of carbazoles substantially as described.

2. The process for the manufacture of fast yellow sulfur dyestuffs, which consists in heating with sulfur at elevated tem eratures in the presence of benzidin hafbgen derivatives of acetylated amino compounds of carlmzoles substantially as described.

3. The process for the manufacture of fast yellow-sulfur dyestuffs, which consists in heatin with sulfur at elevatedtemperatures in t e presence of benzidin acctylated amino compounds ofcarbazoles substituted in the inndo group substantially as described.

4. The process for the manufacture of fast yellow sulfur dyestuffs, which consists in heating, with sulfur at elevated temperatures in the presence of benzidin halogen derivatives of acctylated amino compounds of carbazoles substituted in the imido group substantially as described. v

5. As new articles of manufacture the fast yellow sulfur dyestuffs derived from sulfur and acctylated amino compounds of carbazole being in a dry state yellow to orange powders, insoluble in water and the usual organic solvents, soluble in concentrated sulfuric acid with a reddish brown to a dark brown color, soluble in hot alkaline sulfid solution with an orange-brown color and dyeing vegetable fibers in an alkaline sulfid bath, or in the alkaline hydrosulfite vat yellow shades which are distinguished by their fastness to chlorin, substantially as described.

6. As new articles of manufacture the fast yellow sulfur dyestuffs derived from sulfur and the halogen derivatives of the acetylated amino compounds of earbazole being in a dry state yellow to orange powders, insolable in water and the usual organic solvents, soluble in concentrated sulfuric acid with a reddish brown to a dark brown color, soluble in hot alkaline sullid solution with an orange-brown color and dyeing vegetable fibers in an alkaline sulfid bath or in the alkaline hydrosultite vat yellow shades which are distinguished by their fastness to chlorin, substantially as described.

7. As new articles of manufacture the fast yellow sulfur dyestuffs derived from sulfur and the acetylated amino com )ounds of carbazoles substituted in the llllltlt) group being in a dry state yellow to orange powders, insoluble in water and the usual organic solvents, soluble in concentrated sulfuric acid with a reddish-brown to a dark brown color, soluble in hot alkaline sulfid solution with an orange-brown color and dyeing vegetable fibers in an alkaline sultid bath or in the alkaline hydrosultite vat yellow shades which are distinguished by their fastness to chlorin, substantially as described.

8. As new articles of manufacture the fast yellow sulfur dyestuffs derived from sulfur and the halogen derivatives of the acetylated amino compounds of carbazoles, substituted in the imido group, being in a dry state yellow to orange powders, insoluble in water and the usual organic solvents, soluble in concentrated sulfuric acid with a reddishbrown color and dyeing vegeta ble fibers in brown to a dark brown color, soluble in hot signed our names this 6th day of Feb., 1913,

alkaline sulfid solution .with an orange- 1n the presence of two subscxnbing witnesses. 10

RICHARD HERZ, PH. 1).

an alkaline sulfid bath or in the alkaline WILHELM FROHNEBERG, Pm

hydrosulfite vat yellow shades which are distinguished by their fastness to chlorin, substantially as described.

In witness whereof we have hereunto Witnesses:

JEAN GRUNn, CARL Gmmn.

Ooples of this patent may be obtained for he cents eeeh, by eddreuln: the "Oommluioner of Patents. Washington, D. 0." 

